Alkyl substituted bicyclic monoolefins



United States Patent 3,405,187 ALKYL SUBSTITUTED BICYCLIC MONOOLEFINSHerman S. Bloch, Skokie, Ill., assignor to Universal Oil ProductsCompany, Des Plaines, 11]., a corporation of Delaware No Drawing.Original application Oct. 28, 1964, Ser. No. 407,232. Divided and thisapplication June 28, 1967, Ser. No. 649,459

4 Claims. (Cl. 260-666) ABSTRACT OF THE DISCLOSURE A monoolefin havingfrom about 9 to about 20 carbon atoms is condensed with a conjugatedcyclodiolefin to produce an alkyl substituted bicyclic monoolefinsuitable for use in the manufacture of detergents.

This application is a division of my copending application Ser. No.407,232, filed Oct. 28, 1964, now U.S. Patent 3,370,080, issued Feb. 20,1968.

This invention relates to a novel biodegradable detergent and to aprocess for making the same. More specifically, this invention relatesto a novel detergent whose composition is:

wherein R is an alkyl group of substantially normal character havingfrom 1 to about 17 carbon atoms, R is selected from the group consistingof hydrogen and an alkyl group of substantially normal character havingfrom 1 to about 17 carbon atoms such that the sum of carbon atoms in Rplus R does not exceed 18, R" is (Ch2) where z is 1 or 2 and X is ahydrophilic group. Further, this invention relates to a process for theproduction of the above described novel detergent which comprisescondensing a monoolefin having from about 9 to about 20 carbon atomswith a conjugated cyclodiolefin and introducing a hydrophilic group intothe condensed product. The resulting product which contains both ahydrophilic and a hydrophobic group is a detergent material subject tobacterial attack and degradation in a subsequent sewage treatmentprocess after the detergent has been used in a laundering or othercleaning operation and discharged into such sewage treatment facilities.

One of the major problems prevalent in centers of population throughoutthe world is the disposal of sewage and the inactivation of detergentsdissolved in the sewage in even small quantities. Such disposal problemis especially vexatious in the case of those detergents having analkylaryl structure at the nuclear portion of the detergent molecule.These detergents produce stable foams in hard or soft waters in suchlarge quantities that the foam clogs sewage treatment facilities andoften appears in sufiicient concentration in such facilities to destroythe bacterial necessary for suflicient biological action for propersewage treatment. One of the principal offenders of this type ofdetergent is the alkylaryl sulfonates, which, unlike the fatty acidsoaps, do not precipitate when mixed with hard water containing calciumor magnesium ions in solution. Since these compounds are only partlybiodegradable, the detergent persists in solution and is carried throughthe sewage treatment plant in substantially unchanged or still activeform. Because of the abiding tendency of such detergents to form,especially when mixed 'with aerating devices and stirrers, largequantities of foam are discharged from the sewage digestion plant intorivers and streams where the continuing presence of the detergent ismarked by large billows of foam on the surface. Other offenders of thistype of detergent are the polyoxyalkylated alkylphenols and thepolyoxyalkylated alkylanilines. These same synthetic detergents alsointerfere with the anaerobic process of degradation of other materialssuch as grease, and thus compound further the pollution caused by sewageplant efiluents containing such detergents. These dilute detergentsolutions often enter subsurface water currents which feed intounderground water strata from which many cities draw their watersupplies and these detergents find their way into the water suppliesdrawn from water taps in homes, factories, hospitals and schools.Occasionally these detergents turn up in suflicient quantities in tapwater to make drinking water foam as it pours from the tap.

It is an object of this invention to produce a detergent capable ofbiological degradation during the treatment of sewage containing suchdetergents. It is another object of this invention to provide a processfor making the biodegradable detergent.

It is a more specific object of this invention to produce a detergent ofthe composition:

III

wherein R, R, R" and X are as described hereinbefore.

It is another more specific object of this invention to produce thebiodegradable detergent by condensing a monolefin with a conjugatedcyclodiolefin and introducing a hydrophilic group into the condensedproduct.

One of the starting materials in the process of this invention is amonoolefin preferably of substantially normal character having about 9to 20 carbon atoms per molecule. This material may be prepared by anywell known method such as wax cracking or it may be prepared fromsubstantially normal paraffins. In this latter source, the normalparaffins are separated from hydrocarbon mixture by molecular sieveextraction. The substantially normal paraflin may be reacted with ahalogen selected from the group consisting of chlorine and bromine toform the alkyl halide. The alkyl halide is then dehydrohalogenated to'form the substantially normal monoolefin. The monoolefin has the genericformula RCH=CHR' where R is an alkyl group of substantially normalcharacter having from 1 to about 17 carbon atoms and R is selected fromthe group consisting of hydrogen and an alkyl group of substantiallynormal character having from 1 to about 17 carbon atoms such that thesum of R plus R does not exceed 18.

Another of the starting materials in the process of this invention is aconjugated cyclodiolefin having the generic formula:

the conjugated cyclodiolefin at temperatures of from about 100 C. toabout 250 C. and at pressure of atmospheric or moderatelysuperatmospheric. The thermally condensed product which is a substitutedbicyclic monoolefin is separated and is thereupon converted to a watersoluble, surface active detergent by introducing a hydrophilic groupinto it. The thermal condensation reaction is further illustrated belowwith a generic chemical reaction equation:

The resulting substituted bicyclic monoolefin may be treated in a numberof conventional ways to introduce a hydrophilic group into its structurethereby forming a detergent. For example, the hydrophilic group may be asulfate group, a sulfonate group or a hydroxypolyoxyalkylene group.

The sulfate group may be introduced by reacting the substituted bicyclicmonolefin with concentrated sulfuric acid at temperatures below 50 C.and preferably about C. The resulting sulfate is then neutralized with abasic material, preferably a metal hydroxide or ammonia to form thefinished surface active product. The alkali metals are preferablecations for said metal hydroxide, sodium and potassium being especiallypreferable.

The sulfonate group may be introduced into the substituted bicyclicmonoolefin by hydrohalogenating said bicyclic monoolefin and reactingthe resulting halide with a metal sulfite salt thereby forming thesulfonate. The halogen is preferably selected from the group consistingof chlorine and bromine while the metal sufite is preferably selectedf-rom the group consisting of sodium sufite and potassium sulfite.Alternatively the sulfonate may be for-med by reacting the bicyclicmonoolefin with a metal bisulfite at temperatures of about 100 to 125 C.The metal 'bisulfite is preferably selected from the group consisting ofsodium bisulfite and potassium bisulfite.

Another procedure for introducing hydrophilic groups into thesubstituted bicyclic monoolefin is to hydrate the monoolefin with diluteacid such as sulfuric or hydrofiuoric acid thereby forming thecorresponding alcohol. The alcohol may thereupon be sulfated oroxyethylated to render it water soluble and surface active. This latterstep is accomplished by reacting the alcohol with ethylene oxide in thepresence of a trace amount of a basic material such as sodium acetate,sodium carbonate or sodium hydroxide at temperatures of about 80 C. toform the 'hydrophilic w-hydroxy polyoxyalkylene group.

These and other well known methods and hydrophilic groups may beemployed to form a water soluble, surface active detergent from thesubstituted bicyclic monoolefin. The resulting detergent has thefollowing generic composition:

wherein R is an alkyl group of substantially normal character havingfrom about 1 to about 17 carbon atoms, R is selected from the groupconsisting of hydrogen and an alkyl group of substantially normalcharacter having from 1 to about 17 carbon atoms such that the sum ofcarbon atoms in R plus R does not exceed 18, R" is an alkylene groupwhose formula is (CH and z is 1 or 2 and X is a hydrophilic grouppreferably selected from the group consisting of a sulfate (X is OSO Mwhere M is hydrogen, amine ion or an equivalent of a metal), a sulfonate(X is SO M where M is as defined above), and w-hydroxy polyoxyalkylene[X is -O(C H O) H where n is 2 or 3 and y is a number from S to 30] anda sulfate of an w-hydroxy polyoxyalkylene where n, y and M are asdefined above].

It is to be noted that the relative number of carbon atoms in R and R isdetermined by the position of the double bond in the startingmonoolefin. Thus when the monoolefin is an alpha olefin, then R will behydrogen and R will contain all the carbon atoms in the originalmonoolefin except the two which become part of the cyclic structure.

The resulting detergents are readily degraded by treatment inconventional sewage facilities.

The following examples are presented to illustrate the process of thisinvention but it is not intended to limit the scope of this invention tothe feed materials or products of those specifically shown reactions inthe examples.

Example I A glass liner containing 189 grams (1.5 mole) of 4-nonene, cc.of hexane and 33.1 grams of cyclopentadiene is sealed into an autoclave.The autoclave and contents are heated to a temperature of about 200 C.and maintained at this temperature for a period of about 8 hours at theend of which time the autoclave and contents thereof are cooled to roomtemperature and the desired bicyclic monoolefin is separated by ordinarybatch fractionation. The substituted bicyclic monoolefin is introducedinto a flask which is immersed in a bath maintained at 0 C. Concentratedsulfuric acid at a temperature of 0 C. is introduced into the flask andthe contents thereof thoroughly mixed. The resulting product isthereupon neutralized with sodium hydroxide until a pH of 7 is attained.The product is a crystalline cream colored solid which is completelysoluble in water and shows excellent wetting properties.

EXAMPLE II A mixture of about 252 grams (1.5 mole) of a methyl-3-undecene, 100 cc. of hexane and 40.1 grams of cyclohexadiene is sealedinto an autoclave. The autoclave and contents are heated to atemperature of about 175 C. and maintained at this temperature for aperiod of about 12 hours at the end of which time the autoclave andcontents thereof are cooled to room temperature and the desired bicyclicmonoolefin is separated by ordinary batch fractionation. The substitutedbicyclic monoolefin is hydrated with diluted hydrofluoric acid at 40 C.,to form the corresponding bicyclic alcohol, which is separated andplaced in a glass liner and sealed into an autoclave with 0.5 weightpercent of powdered sodium hydroxide. Sufiicient ethylene oxide ispressured in to result in a ratio of 9 moles of ethylene oxide to 1 moleof bicyclic alcohol. The autoclave and contents are heated to C. andmaintained at that temperature for a period of 2 hours at the end ofwhich time the autoclave and the contents thereof are cooled to roomtemperature and the desired polyoxyethylated detergent is removed. It isfound to have good foaming and detergent properties.

EXAMPLE III A glass liner containing about 420 grams (1.5 mole) of5-eicosene, 200 cc. of hexane and 33.1 grams of cyclopentadiene issealed into an autoclave. The autoclave and contents are heated to atemperature of about C. and maintained at this temperature for a periodof about 16 hours at the end of which time the autoclave and contentsthereof are cooled to room temperature and the desired bicyclicmonoolefin is separated by ordinary batch fractionation. The substitutedbicyclic monoolefin is contacted with anhydrous hydrogen chloride toform the corresponding hydrohalide, and the latter is contacted with anexcess of sodium sulfite by mixing together in a glass flask. Themixture is maintained at 115 C. for one hour whereupon the desiredresulting sulfonate is recovered from the flask. It is a water-soluble,surface-active solid.

I claim:

1. The process for the production of alkyl substituted bicyclicmonoolefins suitable for use in the manufacture of detergent bythermally and noncatalytically condensing a monoolefinic acyclichydrocarbon of from about 9 to about 20 carbon atoms withcyclopentadiene or cyclohexadiene at a temperature of from about 100 C.to about 250 C.

2. The process of claim 1 further characterized in that saidmonoolefinic hydrocarbon is 4-nonene.

3. The process of claim 1 further characterized in that saidmonoolefinic hydrocarbon is a methyl-3-un decene.

4. The process of claim 1 further characterized in that saidmonoolefinic hydrocarbon is S-eicosene.

References Cited UNITED STATES PATENTS DELBERT E. GANTZ, PrimaryExaminer.

V. OKEEFE, Assistant Examiner.

